WO2010113975A1 - Copolymère d'oléfine et de diène conjugué et son procédé de fabrication - Google Patents

Copolymère d'oléfine et de diène conjugué et son procédé de fabrication Download PDF

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WO2010113975A1
WO2010113975A1 PCT/JP2010/055759 JP2010055759W WO2010113975A1 WO 2010113975 A1 WO2010113975 A1 WO 2010113975A1 JP 2010055759 W JP2010055759 W JP 2010055759W WO 2010113975 A1 WO2010113975 A1 WO 2010113975A1
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group
containing group
groups
zirconium dichloride
carbon atoms
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PCT/JP2010/055759
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Japanese (ja)
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憲司 道上
石井　聖一
三谷　誠
武志 狩野
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三井化学株式会社
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Priority to SG2011070323A priority Critical patent/SG174602A1/en
Priority to EP10758746.1A priority patent/EP2415792B1/fr
Priority to CN201080012424.XA priority patent/CN102356100B/zh
Priority to JP2011507234A priority patent/JP5557835B2/ja
Priority to KR1020117024074A priority patent/KR101359198B1/ko
Priority to US13/260,237 priority patent/US8513368B2/en
Publication of WO2010113975A1 publication Critical patent/WO2010113975A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/645—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44, not provided for in a single group of groups C08F4/642 - C08F4/643
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present invention relates to a copolymer of an olefin and a conjugated diene, and a production method thereof.
  • olefin resins such as polyolefins and polyolefin elastomers are excellent in mechanical properties and are used in various fields such as for various molded products.
  • the requirements for physical properties of these olefinic resins have diversified, and olefinic resins with various properties, such as excellent rigidity, impact strength, weather resistance, heat resistance, cold resistance, crosslinking efficiency, oil resistance, and adhesiveness.
  • the appearance of an olefin resin excellent in dyeability, wettability, and compatibility with other polar group-containing resins is desired.
  • Examples of the method include a method of copolymerizing a diene monomer with an olefin, a method of copolymerizing an ⁇ -olefin such as ethylene and a cyclic olefin, and the like.
  • Patent Document 1 Makromol. Chem. 1991, (192), 2591 (Non-patent Document 1), US Pat. No. 6,310,164 (US Pat. 6,310,164) (2001) (Patent Document 2), -080269 (Patent Document 3) and the like.
  • the amount of vinyl groups in the copolymer is not sufficient in any case, or the unsaturated bond contained in the main chain has physical properties such as weather resistance, heat resistance and ozone resistance.
  • There are problems such as lowering the molecular weight and insufficient mechanical properties due to insufficient molecular weight.
  • Non-patent Document 2 discloses a method for synthesizing an ethylene / butadiene copolymer containing a vinyl group and not containing a 1,4-adduct in the main chain.
  • the main chain contains an unsaturated bond derived from a 1,3-adduct, which is not preferable in terms of physical properties.
  • a vinyl group is generated only when the charged ethylene / butadiene ratio is very low, that is, when the charged amount of butadiene is large. Under such conditions, the polymerization activity is remarkably high. It becomes low and is not economically superior in commercial production.
  • Non-Patent Document 2 does not describe the molecular weight measurement result.
  • ethylene / propylene / diene monomer copolymer using ethylidene norbornene, vinyl norbornene, dicyclopentadiene, etc. as the diene monomer has an unsaturated bond in the side chain and is unsaturated in the main chain. It is known as a polyolefin-based elastomer containing no bonds. When these polyolefin-based elastomers are used as rubber moldings, peroxide crosslinking, radical modification, etc. are carried out.
  • the crosslinking method a rubber extruded product containing a vulcanizing agent in advance is batch-treated under pressurized steam. In general, a method of crosslinking by a formula or a method of continuously crosslinking a rubber extruded product previously containing a vulcanizing agent under hot air is employed.
  • a low-boiling-point, low-boiling point general-purpose diene monomer such as 1,3-butadiene
  • a polyolefin-based elastomer having a double bond in the side chain and no unsaturated bond in the main chain and the polyolefin-based
  • the realization of an economically superior process for obtaining elastomers has been sought.
  • a cyclic olefin such as norbornene may be polymerized in the presence of a vanadium catalyst formed from a soluble vanadium compound and an organoaluminum compound.
  • a vanadium catalyst formed from a soluble vanadium compound and an organoaluminum compound.
  • the types of cyclic olefins that can be copolymerized are limited, the polymerization activity is low, and a copolymer having a sufficient molecular weight and cyclic olefin content cannot be obtained, or unreacted cyclic olefins are removed after the reaction. Therefore, there is a problem that it is not economically excellent because a lot of energy is required.
  • ethylene / cyclic olefin (cyclopentene, cyclohexene, cycloheptene, cyclooctene) copolymerization by a catalyst comprising half metallocene and aluminoxane is described in J. Org. Am. Chem. Soc. 2005 (127), 4582 (Non-Patent Document 4), Tetrahedron, 2004 (60), 7147 (Non-Patent Document 5), and the like.
  • ethylene / cyclopentene copolymerization using a catalyst comprising a bisphenoxyimine complex and an aluminoxane is disclosed in Macromolecules, 2002 (35), 9640 (Non-patent Document 6) and the like.
  • these catalyst systems have poor cyclic olefin incorporation efficiency, and in order to obtain a polymer having a high cyclic olefin content, a large amount of cyclic olefin has to be charged, resulting in insufficient polymerization activity.
  • examples of the method for introducing a cyclic structure into the main chain include a method of copolymerizing a diene monomer with an olefin.
  • Such methods are disclosed in Japanese Patent Application Laid-Open No. 11-080269 (Patent Document 5), Japanese Patent Application Laid-Open No. 2004-018697 (Patent Document 6), and the like.
  • Patent Document 5 Japanese Patent Application Laid-Open No. 11-080269
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2004-018697
  • these conventional methods have a problem in that unsaturated bonds contained in the main chain of the resulting copolymer cause deterioration in physical properties such as weather resistance, heat resistance and ozone resistance.
  • Macromolecular Symposia 2006, (234), 1288 (Non-Patent Document 7), Macromolecular Chemistry and Physics, 2006, (207), 304 (Non-Patent Document 8), Macromolecules, 2005, 38, 5493 (Non-Patent Document 9).
  • the main chain has a cyclic structure and is derived from a 1,4-adduct or a 1,3-adduct.
  • the present invention has been made in view of the above-described problems of the prior art, and has a copolymer and a cyclic structure that have a double bond in the side chain and substantially no unsaturated bond in the main chain.
  • Copolymer having substantially no unsaturated bond in the main chain, and low-boiling point ethylene having low-boiling point ethylene and a general-purpose conjugated diene such as 1,3-butadiene It aims to provide a method of economical synthesis by.
  • the present inventors have a double bond in the side chain by copolymerizing at least ethylene and a conjugated diene in the presence of a specific addition polymerization catalyst, In addition, a copolymer that does not substantially contain an unsaturated bond in the main chain or a copolymer that has a cyclic structure in the main chain and does not substantially contain an unsaturated bond in the main chain can be efficiently polymerized.
  • the present invention was completed.
  • the copolymer of the present invention is a copolymer obtained by copolymerizing at least ethylene and a conjugated diene, (1) The proportion of structural units derived from conjugated dienes relative to all monomer units in the copolymer is 1 to 90 mol%, (2) The proportion of structural units derived from 1,2-addition of a conjugated diene having a side chain double bond to the structural units derived from all conjugated dienes in the copolymer is 0 to 90 mol%. The proportion of structural units derived from 1,4-addition of 1,3-cyclopropane is from 0 to 3 mol%, the proportion of structural units derived from 1,3-addition of conjugated dienes is from 0 to 3 mol%.
  • the ratio of the total amount of the structural unit derived from 1,2-addition of a conjugated diene having a skeleton and the structural unit derived from 1,2-addition of a conjugated diene having a 1,2-cyclopentane skeleton is 4 to 100 mol%. It is characterized by being.
  • the ratio of the total amount of the structural unit derived from 1,4-addition of conjugated diene and the structural unit derived from 1,3-addition of conjugated diene to the structural unit derived from all conjugated dienes in the copolymer is 0. It is preferably ⁇ 3 mol%.
  • a structural unit derived from 1,2-addition of a conjugated diene having a 1,2-cyclopropane skeleton and a conjugated diene having a 1,2-cyclopentane skeleton with respect to a structural unit derived from all conjugated dienes in the copolymer The ratio of the total amount of structural units derived from 1,2-addition of is preferably 15 to 99 mol%.
  • the weight average molecular weight of polystyrene conversion measured using the gel permeation chromatography (GPC) of the said copolymer is 20,000 or more. It is preferable that the copolymer has a glass transition point (Tg) of ⁇ 60 to 30 ° C. or no glass transition point, and a melting point (Tm) of 130 ° C. or less or no Tm.
  • GPC gel permeation chromatography
  • the method for producing the copolymer of the present invention is characterized in that at least ethylene and a conjugated diene are copolymerized in the presence of an addition polymerization catalyst comprising the following (A) and (B).
  • a transition metal compound represented by the general formula (I) is preferable.
  • L is a tridentate anion ligand represented by RQ (Pz 1 ) i (Pz 2 ) 3-i , or a neutral ligand;
  • R is hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, silicon-containing group
  • At least 3-position of Pz 1 is substituted with an unsubstituted aryl group, a substituted aryl group, an alkyl group having 3 or more carbon atoms, a cycloalkyl group, an amino group, or an oxyhydrocarbon
  • a pyrazolyl group, Pz 2 is an unsubstituted pyrazolyl group or a substituted pyrazolyl group, i is an integer of 2 or 3, M is a transition metal atom selected from Groups 3 to 11 of the periodic table, X is a hydrogen atom, halogen atom, oxygen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, A silicon-containing group, a germanium-containing group or a tin-containing group, Y is a neutral ligand having an electron donating group, an inorganic salt, an inorganic compound or an organometallic compound, m is a number that satisfies the valence of M; When m is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by
  • (A) is [hydrobis (3-mesitylpyrazol-1-yl) (5-mesitylpyrazol-1-yl)] borate zirconium trichloride, and [hydrotris (3-mesitylpyrazol-1-yl)] It is preferably at least one transition metal compound selected from the group consisting of borate zirconium trichloride.
  • the (A) is preferably a transition metal compound represented by the following general formula (II).
  • R 1 , R 2 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same as or different from each other, and have the same number of carbon atoms.
  • R 9 and R 13 which may be the same or different from each other, are a hydrocarbon group having 6 to 20 carbon atoms, a halogenated hydrocarbon group having 6 to 20 carbon atoms, A silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group is preferred.
  • R 1 and R 5 which may be the same or different from each other, are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, A silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group is preferred.
  • R 9 and R 13 are preferably aromatic groups which may be the same or different from each other.
  • the (A) is preferably a transition metal compound represented by the following general formula (III).
  • R 1 , R 2 and R 3 may be the same or different from each other from hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group.
  • R 4 is selected from a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group;
  • R 1 , R 2 and R 3 are groups selected from hydrocarbon groups, halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups, R 1 and R 4 and R 2 and R 3 are not the same substituent at the same time, R 2 , R 3 , and R 4 may form a ring together with carbon atoms to which a part of groups adjacent to each other are bonded to each other;
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 may be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms Is a halogenated hydrocarbon group of 1 to 20, a
  • R 1 , R 2 , R 13 , R 14 , R 15 , and R 16 which may be the same or different from each other, are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, and 1 to Selected from 20 halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups; R 13 , R 14 , R 15 , and R 16 may form a ring together with carbon atoms to which a part of groups adjacent to each other are bonded to each other; R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 may be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms Is a halogenated hydrocarbon group of 1 to 20, a silicon-containing group, an oxygen-containing group, a sulfur-containing
  • R 1 and R 13 which may be the same or different from each other, are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, A silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group is preferred.
  • R 6 , R 7 , R 10 , and R 11 may form a ring together with carbon atoms to which a part of groups adjacent to each other are bonded to each other.
  • Hydrocarbon groups having 1 to 20 carbon atoms, halogenated hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, which may be the same or different from each other A group or a phosphorus-containing group is preferred.
  • R 6 , R 7 , R 10 , and R 11 may form a ring together with carbon atoms to which a part of groups adjacent to each other are bonded to each other.
  • R 1 , R 13 , R 6 , R 7 , R 10 , and R 11 are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group , An oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group.
  • R 13 is preferably an aromatic group.
  • the (A) is also preferably a transition metal compound represented by the following general formula (V).
  • M represents a transition metal atom in groups 4 to 6 of the periodic table
  • R 1 and R 3 are hydrogen
  • R 2 and R 4 may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, Selected from sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms Is a halogenated hydrocarbon group of 1 to 20, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom, and a part of the groups adjacent to each other is
  • R 6 , R 7 , R 10 , and R 11 may form a ring together with carbon atoms to which a part of groups adjacent to each other are bonded to each other.
  • Hydrocarbon groups having 1 to 20 carbon atoms, halogenated hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, which may be the same or different from each other A group or a phosphorus-containing group is preferred.
  • the copolymer of the present invention substantially free of unsaturated bonds in the main chain and having a cyclic structure in the main chain is excellent in weather resistance, heat resistance, oil resistance, cold resistance, etc., has a low glass transition point and cold resistance. Excellent in properties.
  • the copolymer of the present invention, which contains substantially no unsaturated bond in the main chain has a cyclic structure in the main chain, and has a double bond in the side chain, has weather resistance, heat resistance, oil resistance, etc.
  • the glass transition point is low, the cold resistance is excellent, the crosslinking efficiency and the modification efficiency are excellent, especially the crosslinking efficiency and the modification efficiency when an organic peroxide is used, and sulfur crosslinking is also possible.
  • the cross-linked product obtained using organic peroxide has low adhesiveness on the cross-linked product surface, no abnormal foaming inside, and heat aging resistance (heat resistance) and sag resistance. Also excellent.
  • the method for producing a copolymer of the present invention can industrially produce the above copolymer at low cost and economical efficiency.
  • the copolymer of the present invention is a copolymer obtained by copolymerizing at least ethylene and a conjugated diene, (1) The proportion of structural units derived from conjugated dienes relative to all monomer units in the copolymer is 1 to 90 mol%, (2) The proportion of structural units derived from 1,2-addition of a conjugated diene having a side chain double bond to the structural units derived from all conjugated dienes in the copolymer is 0 to 90 mol%.
  • the proportion of structural units derived from 1,4-addition of 1,3-cyclopropane is from 0 to 3 mol%
  • the proportion of structural units derived from 1,3-addition of conjugated dienes is from 0 to 3 mol%.
  • the ratio of the total amount of the structural unit derived from 1,2-addition of a conjugated diene having a skeleton and the structural unit derived from 1,2-addition of a conjugated diene having a 1,2-cyclopentane skeleton is 4 to 100 mol%. It is characterized by being.
  • the copolymer of the present invention is also referred to as a copolymer of olefin and conjugated diene.
  • the double bond which exists in a side chain is also described as a side chain double bond.
  • the side chain double bond is a carbon / carbon double bond derived from a conjugated diene.
  • the proportion of structural units derived from conjugated dienes relative to all monomer units in the copolymer refers to the proportion of structural units derived from conjugated dienes in 100 mol% of all monomer units in the copolymer. .
  • ratio of structural unit derived from 1,2-addition of conjugated diene having a side chain double bond to structural unit derived from all conjugated dienes in the copolymer, derived from 1,4-addition of conjugated diene Of structural units derived from 1,3-addition of conjugated dienes, structural units derived from 1,2-addition of conjugated dienes having a 1,2-cyclopropane skeleton, and 1,2-cyclo
  • the ratio of the total amount of structural units derived from 1,2-addition of a conjugated diene having a pentane skeleton each has a side chain double bond in 100 mol% of structural units derived from all conjugated dienes in the copolymer.
  • the proportion of structural units derived from 1,2-addition of conjugated dienes, the proportion of structural units derived from 1,4-addition of conjugated dienes, the proportion of structural units derived from 1,3-addition of conjugated dienes, 1, 2-cyclopropane It indicates the percentage of the total amount of structural units derived from the 1,2-addition of conjugated dienes having a structural unit and 1,2-cyclopentane skeleton derived from 1,2-addition of conjugated dienes having a rating.
  • the copolymer of olefin and conjugated diene of the present invention usually has a structural unit derived from ethylene and a structural unit derived from conjugated diene.
  • the structural unit derived from a conjugated diene that the copolymer of the present invention has is a structural unit derived from 1,2-addition (including 3,4-addition) of a conjugated diene having a side chain double bond, 1, Structural units derived from 1,2-addition (including 3,4-addition) of conjugated dienes having a 2-cyclopropane skeleton, 1,2-addition of conjugated dienes having a 1,2-cyclopentane skeleton (3,3) 4-containing inclusions).
  • the structural unit derived from 1,2-addition (including 3,4-addition) of a conjugated diene having a 1,2-cyclopropane skeleton refers to 1,2-addition (3 , 4-addition), and a 1,2-addition (including a 3,4-addition) of a conjugated diene having a 1,2-cyclopentane skeleton.
  • 1,2-addition including 3,4-addition
  • the copolymer of the present invention substantially includes a structural unit derived from 1,4-addition of a conjugated diene and a structural unit derived from 1,3-addition of a conjugated diene as a structural unit derived from a conjugated diene.
  • the ratio of the structural unit derived from 1,4-addition of conjugated diene to the structural unit derived from all conjugated dienes in the copolymer is 0 to 3 mol%.
  • the proportion of structural units derived from 1,3-addition is 0 to 3 mol%.
  • 1,2-addition includes not only 1,2-addition but also 3,4-addition.
  • the proportion of structural units derived from conjugated dienes relative to all monomer units in the copolymer is 1 to 90 mol%, preferably 6 to 80 mol%, more preferably 7 to 80 mol%.
  • the proportion of structural units derived from ethylene to the total monomer units in the copolymer is usually 10 to 99 mol%, preferably 20 to 94 mol%, more preferably 20 ⁇ 93 mol%.
  • the proportion of structural units derived from 1,2-addition of a conjugated diene having a side chain double bond to the structural units derived from all conjugated dienes in the copolymer is 0 to 90 mol%. It is preferably 0.5 to 90 mol%, more preferably 1 to 80 mol%.
  • the ratio of the structural unit derived from 1,4-addition of conjugated diene to the structural unit derived from all conjugated dienes in the copolymer is 0 to 3 mol%.
  • the proportion of structural units derived from 1,3-addition is 0 to 3 mol%, preferably structural units derived from 1,4-addition of conjugated dienes, and structural units derived from 1,3-addition of conjugated dienes.
  • the proportion of the total amount is 0 to 3 mol%, more preferably the proportion of structural units derived from 1,4-addition of conjugated diene is 0 mol%, and the proportion of structural units derived from 1,3-addition of conjugated diene
  • the ratio is 0 mol% (that is, the ratio of the total amount of structural units derived from 1,4-addition of conjugated diene and structural units derived from 1,3-addition of conjugated diene is 0 mol%).
  • the amount of structural unit derived from 1,4-addition of conjugated diene and structural unit derived from 1,3-addition of conjugated diene is within the above range with respect to structural units derived from all conjugated dienes in the copolymer. And the weather resistance, heat resistance, crosslinking efficiency, cold resistance, and modification efficiency of the copolymer are desirable. Within the above range, the copolymer is also excellent in properties such as ozone resistance, heat aging resistance, low temperature characteristics, and dynamic fatigue resistance.
  • the copolymer of the present invention includes a structural unit derived from 1,2-addition of a conjugated diene having a 1,2-cyclopropane skeleton and a 1,2-cyclopentane skeleton with respect to a structural unit derived from all conjugated dienes.
  • the 1,2-cyclopropane skeleton is a cis or trans 3-membered ring (cyclopropane ring), and the 1,2-cyclopentane skeleton is a cis or trans 5-membered ring (cyclopentane ring). is there.
  • the copolymer of the present invention has at least one of a 1,2-cyclopropane skeleton and a 1,2-cyclopentane skeleton, and may have both.
  • the copolymer of the present invention preferably has a polystyrene equivalent weight average molecular weight (Mw; polystyrene equivalent) measured by gel permeation chromatography (GPC) of 20,000 or more.
  • Mw polystyrene equivalent weight average molecular weight
  • GPC gel permeation chromatography
  • the upper limit of the weight average molecular weight is not particularly limited, but the weight average molecular weight of the copolymer is usually 10,000,000 or less.
  • the weight average molecular weight of the copolymer is more preferably 40,000 to 5,000,000.
  • the mechanical strength of the copolymer of the present invention may be inferior.
  • the copolymer of the present invention is inferior in adhesiveness or compatibility with other resins. There is.
  • the molecular weight distribution (Mw / Mn (weight average molecular weight / number average molecular weight)) determined from the polystyrene-equivalent weight average molecular weight and the polystyrene-equivalent number average molecular weight is usually 15.0 or less and 10.0 or less. Preferably, it is 9.0 or less, more preferably 5.0 or less.
  • the copolymer of the present invention usually has a glass transition point (Tg) measured with a differential scanning calorimeter (DSC) of ⁇ 60 to 30 ° C. or no glass transition point.
  • the glass transition point is preferably ⁇ 60 to 0 ° C., more preferably ⁇ 60 to ⁇ 10 ° C.
  • the copolymer of the present invention usually has a melting point (Tm) measured by the same measurement of 130 ° C. or lower or no melting point. When it has a melting point, the upper limit of the melting point is preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
  • fusing point there is no limitation in particular as a minimum of melting
  • the copolymer of the present invention is obtained by copolymerizing at least ethylene and a conjugated diene as described above. Although there is no limitation in particular as a conjugated diene, Usually, what is represented by following formula (i) is used.
  • R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and at least one of R 1 and R 2 is a hydrogen atom.
  • Such a conjugated diene monomer (i) may be either aromatic or aliphatic, and is not particularly limited.
  • conjugated dienes include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3-butadiene, 1- Phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene, Examples include 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, and 2-phenyl-1,3-butadiene.
  • the conjugated dienes can be used alone or in combination of two or more.
  • 1,3-butadiene is particularly preferable because it is inexpensive and has excellent copolymerizability and crosslinking efficiency.
  • the copolymer of the present invention has a vinyl group in the side chain as a side chain double bond.
  • the copolymer of the present invention may further use other monomers in addition to ethylene and conjugated dienes.
  • the other monomer include ⁇ -olefins having 3 to 20 carbon atoms and derivatives thereof, nonconjugated dienes and derivatives thereof, nonconjugated polyenes and derivatives thereof, and styrene and derivatives thereof.
  • Examples of the ⁇ -olefin having 3 to 20 carbon atoms and derivatives thereof include propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, -Undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl ⁇ -olefins such as -1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, and 3-phenyl Examples thereof include ⁇ -olefin derivatives such as propylene and 4-phenylbutene.
  • Styrene and its derivatives include mono- or poly-styrene such as styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, etc.
  • Alkyl styrene methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene and other functional group-containing styrene derivatives: ⁇ -methylstyrene, etc. Is mentioned.
  • Non-conjugated dienes and their derivatives include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene and the like.
  • non-conjugated polyene and derivatives thereof examples include 5,9-dimethyl-1,4,8-decatriene. These other monomers can be used alone or in combination of two or more.
  • the ratio of the structural unit derived from the other monomer to the total monomer unit may be more than 0 mol% and not more than 60 mol%.
  • the structural unit derived from another monomer is preferably a structural unit derived from at least one monomer selected from the group consisting of ⁇ -olefins having 3 to 20 carbon atoms and derivatives thereof, styrene and derivatives thereof. .
  • the copolymer of the present invention is excellent in properties such as surface hardness, wear resistance, anti-vibration properties, braking properties, weather resistance, ozone resistance, heat aging resistance, low temperature properties, and dynamic fatigue resistance. Good compatibility with polar resins and fillers. Therefore, the copolymer of the present invention can be used for various molded products such as automobile parts.
  • the method for producing a copolymer of the present invention is a method for producing the aforementioned copolymer.
  • the method for producing a copolymer of the present invention comprises the step of copolymerizing at least ethylene and a conjugated diene in the presence of an addition polymerization catalyst comprising the following (A) and (B): It is a manufacturing method.
  • component (B) transition metal compound having a transition metal atom selected from Groups 3 to 11 of the periodic table
  • B (B-1) organometallic compound, At least one compound selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound that reacts with the transition metal compound (A) to form an ion pair.
  • Component (A) and the above (B) are also referred to as component (B).
  • the copolymer of this invention is a copolymer obtained by copolymerizing ethylene and conjugated diene
  • the reaction other than copolymerization here include, for example, 1,4-addition of conjugated diene to a structural unit derived from all conjugated dienes in a copolymer obtained by copolymerizing ethylene and conjugated diene.
  • a hydrogenation reaction in which hydrogen is added to a copolymer in which the proportion of the total amount of structural units derived from 1,3-addition of a conjugated diene exceeds 3 mol%.
  • the addition polymerization catalyst used in the method for producing a copolymer of the present invention contains a transition metal compound (A) having a transition metal atom selected from Groups 3 to 11 of the periodic table.
  • transition metal compound (A) having a transition metal atom selected from Groups 3 to 11 of the periodic table transition metal compounds represented by the following general formulas (I) to (V) are preferable.
  • a transition metal compound (A) it is normally used individually by 1 type, However, You may use it in combination of 2 or more type.
  • L is a tridentate anion ligand represented by RQ (Pz 1 ) i (Pz 2 ) 3-i , or a neutral ligand;
  • R is hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, silicon-containing group
  • At least 3-position of Pz 1 is substituted with an unsubstituted aryl group, a substituted aryl group, an alkyl group having 3 or more carbon atoms, a cycl
  • a pyrazolyl group, Pz 2 is an unsubstituted pyrazolyl group or a substituted pyrazolyl group, i is an integer of 2 or 3, M is a transition metal atom selected from Groups 3 to 11 of the periodic table, X is a hydrogen atom, halogen atom, oxygen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, A silicon-containing group, a germanium-containing group or a tin-containing group, Y is a neutral ligand having an electron donating group, an inorganic salt, an inorganic compound or an organometallic compound, m is a number that satisfies the valence of M; When m is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by
  • R represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, or a phosphorus-containing group.
  • Halogen atom hydrocarbon group, heterocyclic compound residue, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, silicon-containing group, germanium-containing group,
  • tin-containing group include the groups exemplified in the description of X in the general formula (I).
  • Q is an atom selected from the group consisting of boron, carbon, silicon, germanium, tin, and lead, and is preferably an atom selected from the group consisting of boron, carbon, and silicon.
  • At least the 3-position of Pz 1 is an unsubstituted aryl (Aryl) group, a substituted aryl (Aryl) group, an alkyl group having 3 or more carbon atoms, a cycloalkyl group, an amino group. Or a pyrazolyl group substituted with an oxyhydrocarbon group or the like.
  • the unsubstituted aryl (Aryl) group include a phenyl group, a naphthyl group, and a fluorenyl group.
  • the substituted aryl (Aryl) group includes a nucleus of the unsubstituted aryl (Aryl) group. Examples thereof include one in which one or more hydrogen atoms are substituted with an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group.
  • the 3-position is a 2,4,6-trimethylphenyl (2,4,6-Trimethylphenyl) group, a 2,4,6-triisopropylphenyl (2,4,6-Triisopropylphenyl) group, , 3,4,5,6-pentamethylphenyl (2,3,4,5,6-pentamethylphenyl) group, 4-tert-butyl-2,6-dimethylphenyl (4-Tert-Butyl-2,6- A pyrazolyl group substituted with a dimethylphenyl) group, and a pyrazolyl group substituted with a 2,4,6-trimethylphenyl group at the 3-position is particularly preferred.
  • Pz 2 represents an unsubstituted pyrazolyl group or a substituted pyrazolyl group.
  • the substituted pyrazolyl group may be the same as the above-mentioned Pz 1, and further may be a group in which the group exemplified as the substituent of the substituted aryl group is substituted at any position other than the 3-position.
  • i is 2 or 3.
  • Specific examples of the transition metal compound represented by the general formula (I) include [hydrobis (3-mesitylpyrazol-1-yl) (5-mesitylpyrazol-1-yl)] borate zirconium trichloride [hydrobis (3 -Mesylpyrazol-1-yl) (5-mesylpyrazol-1-yl)] borate zirconium trichloride), potassium [[hydrobis (3-mesitylpyrazol-1-yl) (5-mesitylpyrazol-1-yl)] borate Titanium (III) trichloride] (potassium [[hydrobis (3-mesylpyrazol-1-yl) (5-mesylpyrazol-1-yl)] borate titanium (III) trich loride]), [hydrobis (3-mesitylpyrazol-1-yl) (5-mesitylpyrazol-1-yl)] borate hafnium trichlor
  • the general formula (I) may form a complex such as a dimer, trimer or oligomer via the neutral ligand Y, or alternatively, via these neutral ligands, For example, a cross-linked structure such as a ⁇ -oxo compound may be formed.
  • the transition metal compound represented by the general formula (I) is shown below.
  • the methyl group is Me
  • the t-butyl group is t-Bu
  • the n-butyl group is n-Bu
  • the trimethylsilyl group is TMS
  • the phenyl group is Ph
  • the mesityl group (2,4,6-trimethyl). Phenyl group) may be abbreviated as Ms.
  • the transition metal compound represented by the general formula (I) reacts, for example, a metal salt (a) represented by the following general formula (X) with a transition metal salt (b) represented by the following general formula (Y). Can be manufactured.
  • a metal salt (a) represented by the following general formula (X) with a transition metal salt (b) represented by the following general formula (Y).
  • Y transition metal salt
  • a purification step of separating the regioisomer of the metal salt (a) using a chromatograph in which the filler is neutral or basic is included.
  • Z represents a metal atom selected from Group 1, Group 13, and Group 14 of the Periodic Table, preferably potassium element, sodium element, thallium element, tin element, Preferably it is a thallium element.
  • j represents an integer of 0 or 1, and is preferably 1.
  • L is the same as L in the general formula (I).
  • M, X, Y, m, and n are the same as M, X, Y, m, and n in the general formula (I).
  • the transition metal compound represented by the general formula (I) is represented by the metal salt (a) represented by the general formula (X) and the general formula (Y) while being dissolved or suspended in a nonpolar solvent. It is preferable to react the transition metal salt (b).
  • the nonpolar solvent include petroleum ether, hexane, carbon tetrachloride, carbon disulfide, toluene, benzene and the like, preferably toluene, benzene and the like.
  • the manufacturing method of the transition metal compound represented by general formula (I) is demonstrated with a specific example.
  • it is a precursor of a transition metal compound represented by the general formula (I), and the 3-position which is a kind of the metal salt (a) is substituted with an unsubstituted aryl (Aryl) group or a substituted aryl (Aryl) group
  • the 3-position which is a kind of the metal salt (a) is substituted with an unsubstituted aryl (Aryl) group or a substituted aryl (Aryl) group
  • Synthesis of thallium complexes with trispyrazolyl borate ligands having two or more pyrazolyl groups is described in Inorg. Chem. 1993 (32), 3471, etc., or similar methods.
  • the silica gel can be stirred in an eluent containing triethylamine.
  • the eluent for performing flash column chromatography is not particularly limited.
  • examples thereof include ethyl, acetone, ethanol, methanol, or a mixed solution thereof.
  • the transition metal salt (b) is added to the pure thallium complex thus obtained, and then a nonpolar solvent is added and reacted with stirring.
  • the liquid temperature during the reaction is in the range of ⁇ 80 ° C. to 120 ° C., preferably ⁇ 30 to 30 ° C. is selected.
  • the nonpolar solvent to be used include petroleum ether, hexane, carbon tetrachloride, carbon disulfide, toluene, benzene and the like, and preferably toluene, benzene and the like as described above.
  • normal operations used when purifying the transition metal compound such as extraction and recrystallization are used. used.
  • M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, specifically, a Group 3 metal atom such as scandium, yttrium, lanthanoids, actinoids, titanium, Group 4 metal atoms such as zirconium and hafnium; Group 5 metal atoms such as vanadium, niobium and tantalum; Group 6 metal atoms such as chromium, molybdenum and tungsten; Group 7 metal atoms such as manganese, technetium and rhenium; Group 8 metal atoms such as iron, ruthenium and osmium; Group 9 metal atoms such as cobalt, rhodium and iridium; Group 10 metal atoms such as nickel, palla
  • Group 3 metal atoms, Group 4 metal atoms, Group 5 metal atoms, and Group 6 metal atoms are preferable, and transition metals such as yttrium, titanium, zirconium, hafnium, vanadium, and chromium are preferable.
  • the transition metal atom M is more preferably a transition metal atom of Group 4 or Group 5 of the periodic table in which the valence state is divalent, trivalent or tetravalent, and is made of titanium, zirconium or hafnium. Particularly preferred is zirconium, and most preferred is zirconium.
  • the transition metal atom M is titanium or vanadium, it is particularly preferable that it is trivalent.
  • X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, A silicon-containing group, a germanium-containing group or a tin-containing group is shown.
  • M and X are bonded by a double bond.
  • halogen atom examples include fluorine, chlorine, bromine and iodine.
  • hydrocarbon group examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cycloalkyl having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl Groups; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl And aryl groups such as phenanthryl
  • oxygen-containing group examples include an oxy group; a peroxy group; a hydroxy group; a hydroperoxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; Arylalkoxy groups such as phenylethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like.
  • sulfur-containing group examples include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl benzene sulfonate, triisobutyl benzene sulfonate, Sulfonate groups such as p-chlorobenzene sulfonate and pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene Sulfinate groups such as sulfinates; alkylthio groups; arylthio groups; sulfate groups; sulfide groups; polysulfide groups;
  • nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino
  • Arylamino group or alkylarylamino group such as: trimethylamine, triethylamine, triphenylamine, N, N, N ′, N′-tetramethylethylenediamine (tmeda), N, N, N ′, N′-tetraphenylpropylenediamine Alkyl or arylamine groups such as (tppda).
  • boron-containing group examples include BR 4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, or a halogen atom).
  • aluminum-containing group examples include AlR 4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, or a halogen atom).
  • the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups and the like.
  • trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine
  • triarylphosphine groups such as triphenylphosphine and tolylphosphine
  • halogen-containing group examples include fluorine-containing groups such as PF 6 and BF 4 , chlorine-containing groups such as ClO 4 and SbCl 6, and iodine-containing groups such as IO 4 .
  • a halogenated hydrocarbon group in which at least one hydrogen of the hydrocarbon group is substituted with a halogen.
  • halogenated hydrocarbon group examples include groups in which at least one hydrogen atom of a hydrocarbon group having 1 to 30 carbon atoms is halogen-substituted, and at least one hydrocarbon group having 1 to 20 carbon atoms is included.
  • a group in which hydrogen is halogen-substituted is preferable.
  • heterocyclic compound residue examples include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and the like.
  • residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and the like.
  • examples include a group obtained by further substituting a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, into the heterocyclic compound residue.
  • silicon-containing groups include hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl.
  • Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl;
  • germanium-containing group examples include groups in which silicon in the silicon-containing group is replaced with germanium.
  • tin-containing group examples include groups in which silicon in the silicon-containing group is substituted with tin.
  • a plurality of atoms or groups represented by X may be the same or different from each other as described above, and a plurality of groups represented by X may be bonded to each other to form a ring.
  • m is a number that satisfies the valence of M, is determined by the valence of the transition metal atom M and the valence of X, and is such a number that these positive and negative valences are neutralized.
  • the absolute value of the valence of the transition metal atom M is a and the absolute value of the valence of X is b
  • Y represents a neutral ligand having an electron donating group, an inorganic salt, an inorganic compound, or an organometallic compound
  • n representing the number of Y is an integer of 0 to 3 And preferably 1 or 2.
  • the electron donating group is a group having an unpaired electron that can be donated to a metal, and Y may be any neutral ligand as long as it has an electron donating property.
  • Y include linear or cyclic saturated or unsaturated ethers such as diethyl ether, dimethyl ether, diisopropyl ether, tetrahydrofuran, furan, dimethylfuran, anisole, diphenyl ether, and methyl-t-butyl ether, such as acetaldehyde, Linear or cyclic saturated or unsaturated aldehydes such as propionaldehyde, n-butyraldehyde, benzaldehyde, p-nitrobenzaldehyde, p-tolualdehyde, phenylacetaldehyde, such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, acetophenone, Linear or cyclic saturated or unsaturated ketones such as benzophenone, n-butyrophenone, benzyl methyl ketone, such as formamide, acetamide, Linear or
  • Nitrogen heterocyclic compounds for example, sulfur-containing heterocyclic compounds such as thiophene and thiazole, for example, phosphines to be retained such as trimethylphosphine, triethylphosphine, tri-n-butylphosphine, triphenylphosphine, for example acetonitrile, benzonitrile Saturated or unsaturated nitriles such as, for example, inorganic salts such as lithium chloride, sodium chloride, potassium chloride, magnesium chloride and calcium chloride, inorganic compounds such as carbon monoxide and carbon dioxide, such as those described later in (B-1) Organic metal Compounds and the like.
  • phosphines to be retained such as trimethylphosphine, triethylphosphine, tri-n-butylphosphine, triphenylphosphine, for example acetonitrile, benzonitrile Saturated or unsaturated nitriles such as, for
  • Y in the above formula (I) is preferably an unsaturated ether, an unsaturated aldehyde, an unsaturated ketone, a nitrogen-containing heterocyclic compound, or an inorganic salt.
  • R 1 , R 2 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same as or different from each other, and have the same number of carbon atoms.
  • M is a transition metal atom in Groups 4 to 6 of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten, Titanium, zirconium or hafnium is preferred, and zirconium is particularly preferred.
  • R 1 , R 2 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are the same or different from each other.
  • R 9 and R 13 which may be the same or different from each other, are a hydrocarbon group having 6 to 20 carbon atoms, a halogenated hydrocarbon group having 6 to 20 carbon atoms, A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group is preferred from the viewpoints of improving activity and improving molecular weight.
  • R 1 and R 5 which may be the same or different from each other, are a hydrocarbon group having 1 to 20 carbon atoms and a halogenated hydrocarbon having 1 to 20 carbon atoms. From the viewpoint of improving activity and improving molecular weight, it is preferably any of a group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group.
  • R 9 and R 13 may be the same or different from each other and are preferably aromatic groups from the viewpoints of improving activity and improving molecular weight.
  • the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n -Alkyl groups such as hexyl and cyclohexyl, alkenyl groups such as vinyl and propenyl, phenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphen
  • halogenated hydrocarbon group having 1 to 20 carbon atoms for example, at least one hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms such as trifluoromethyl, fluorine, chlorine A group substituted with a halogen atom such as bromine, iodine, or 6 carbon atoms such as 2,3,4,5,6-pentafluorophenyl, 3,5-difluorophenyl, 3,5-ditrifluoromethylphenyl, etc. ⁇ 20 halogenated aryl groups and the like.
  • silicon-containing group examples include hydrocarbon group-substituted silyl groups such as trimethylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, triphenylsilyl, and those having 1 to 20 carbon atoms.
  • oxygen-containing group examples include an oxy group; a peroxy group; a hydroxy group; a hydroperoxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; Arylalkoxy groups such as phenylethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like.
  • the sulfur-containing group includes a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl Sulfonate groups such as benzene sulfonate, triisobutyl benzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene Sulphinate groups such as ruffinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio group; arylthio group; sulfate group; sulfide
  • nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino An arylamino group such as methylimino, ethylimino group, i-propylimino group, tert-butylimino group, etc .; phenylimino, 2-methylphenylimino group, 2,6-dimethylphenylimino group 2,4,6-trimethylphenylimino group, 2-i-propylphenylimino group, 2,6-di-i-propylphenylimino group, 2,4,6-tri-i-propylphenylimino group, 2 -Tert-Buchi Arylimino groups such as
  • the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups and the like.
  • trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine
  • triarylphosphine groups such as triphenylphosphine and tolylphosphine
  • R 2 , R 6 , R 10 , R 11 , R 12 , R 14 , R 15 and R 16 may be the same as or different from each other, a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms It is preferable that
  • X 1 and X 2 are a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, which may be the same or different from each other.
  • the hydrocarbon group carbon that can be used as R 1 , R 2 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16. Examples thereof include hydrocarbon groups having 1 to 20 atoms.
  • halogenated hydrocarbon group examples include R 1 , R 2 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , R 13 , R And halogenated hydrocarbon groups having 1 to 20 carbon atoms that can be used as 14 , R 15 and R 16 .
  • oxygen-containing groups examples include hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy, and arylalkoxy groups such as phenylmethoxy and phenylethoxy. It is done.
  • sulfur-containing group examples include a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, and p-toluene.
  • Sulfonate groups such as sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methyl sulfonate
  • Sulfinate groups such as finate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate and pentafluorobenzene sulfinate.
  • silicon-containing group examples include hydrocarbon group-substituted silyl groups such as trimethylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, triphenylsilyl, and those having 1 to 20 carbon atoms.
  • X1 and X2 are preferably a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a halogen atom, which may be the same or different from each other, and more preferably Are each independently a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • Y represents a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, —O—, —CO—, —S —, —SO—, —SO 2 —, —Ge—, —Sn—, —NR—, —P (R) —, —P (O) (R) —, —BR— or —AlR— [wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, or an alkoxy group.
  • the divalent hydrocarbon group is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, Alkylene groups such as 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, arylalkylene groups such as diphenylmethylene, diphenyl-1,2-ethylene, etc. Can be mentioned.
  • divalent hydrocarbon groups include dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, An alkylene group such as 1,4-cyclohexylene and an arylalkylene group such as diphenylmethylene and diphenyl-1,2-ethylene are preferred.
  • the divalent halogenated hydrocarbon group is preferably a halogenated hydrocarbon group obtained by halogenating the divalent hydrocarbon group having 1 to 20 carbon atoms.
  • a halogenated hydrocarbon group obtained by halogenating the divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene.
  • divalent silicon-containing groups include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (iso-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p Alkyltolylene such as -tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, alkyldisilyl such as tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl, Alkyl aryl disilyl, aryl disilyl group and the like can be mentioned.
  • divalent germanium-containing group examples include groups in which silicon of the divalent silicon-containing group is replaced with germanium.
  • divalent tin-containing group examples include groups in which the silicon of the divalent silicon-containing group is substituted with tin.
  • R is a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, or an alkoxy group.
  • R is a hydrocarbon group or a halogenated hydrocarbon group
  • the same groups as the hydrocarbon groups and halogenated hydrocarbon groups exemplified for X1 and X2 can be used.
  • R is an alkoxy group, an alkoxy group such as methoxy, ethoxy, propoxy, or butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, or naphthoxy; an arylalkoxy group such as phenylmethoxy or phenylethoxy is used. be able to.
  • transition metal compound represented by the general formula (II) Specific examples of the transition metal compound represented by the general formula (II) are shown below.
  • the transition metal compound represented by the general formula (II) rac-dimethylsilyl-bis ⁇ 1- (2-methyl-4-phenylindenyl) ⁇ zirconium dichloride, rac-dimethylsilyl-bis ⁇ 1- (2-methyl-4- ( ⁇ -naphthyl) indenyl) ⁇ zirconium dichloride, rac-dimethylsilyl-bis ⁇ 1- (2-methyl-4- ( ⁇ -naphthyl) indenyl) ⁇ zirconium dichloride, rac-dimethylsilyl-bis ⁇ 1- (2-methyl-4- (2-methyl-1-naphthyl) indenyl) ⁇ zirconium dichloride, rac-dimethylsilyl-bis ⁇ 1- (2-methyl-4- (5-acenaphthyl) indeny
  • transition metal compound represented by the general formula (II) a transition metal compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten in the above examples of compounds may be used. it can.
  • transition metal compound represented by the above general formula (II) is Journal of Organometallic Chem. 288 (1985), pp. 63-67, European Patent Application Publication No. 320762, Japanese Patent Laid-Open No. 4-268307, European Patent Application Publication No. 549900, European Patent Application Publication No. 576970, Europe It can be produced according to the methods described in Japanese Patent Application No. 6296632 and CA2084017.
  • transition metal compound represented by the above general formula (II) is usually used as a catalyst component for olefin polymerization as a racemate, but R-type or S-type can also be used.
  • Transition metal compounds represented by general formulas (III) to (V) are usually used as a catalyst component for olefin polymerization as a racemate, but R-type or S-type can also be used.
  • R 1 , R 2 and R 3 may be the same or different from each other from hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group.
  • R 4 is selected from a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group;
  • R 1 , R 2 and R 3 are groups selected from hydrocarbon groups, halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups, R 1 and R 4 and R 2 and R 3 are not the same substituent at the same time, R 2 , R 3 , and R 4 may form a ring together with carbon atoms to which a part of groups adjacent to each other are bonded to each other;
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 may be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms Is a halogenated hydrocarbon group of 1 to 20, a
  • R 1 , R 2 , R 13 , R 14 , R 15 , and R 16 which may be the same or different from each other, are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, and 1 to Selected from 20 halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups; R 13 , R 14 , R 15 , and R 16 may form a ring together with carbon atoms to which a part of groups adjacent to each other are bonded to each other; R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 may be the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms Is a halogenated hydrocarbon group of 1 to 20, a silicon-containing group, an oxygen-containing group, a sulfur-containing
  • M represents a transition metal atom in groups 4 to 6 of the periodic table
  • R 1 and R 3 are hydrogen
  • R 2 and R 4 may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, Selected from sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms Is a halogenated hydrocarbon group of 1 to 20, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom, and a part of the groups adjacent to each other is
  • the transition metal compound represented by the general formula (V) is a compound that can be suitably used in the present invention among the transition metal compounds represented by the general formula (III).
  • M is a transition metal atom in Groups 4 to 6 of the periodic table. Specifically, M is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably titanium, zirconium or hafnium, particularly preferably zirconium.
  • R 1 , R 2 , and R 3 may be the same or different from each other, hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, selected from a nitrogen-containing group or a phosphorus-containing group
  • R 4 is selected from a hydrocarbon group, halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R 1,
  • R 2 and R 3 are a group selected from a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group
  • R 1 and R 4 , and R 2 and R 3 are not the same substituent at the same time, and R 2 , R 3 and R 4 may form a ring together with the carbon atoms to which a part of the groups adjacent to each other
  • R 1 and R 3 are hydrogen
  • R 2 and R 4 may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms Is selected from 1 to 20 halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, and phosphorus-containing groups.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 may be the same as or different from each other, and the number of carbon atoms Is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom
  • a part of groups adjacent to each other may be bonded to form a ring together with the carbon atom to which these groups are bonded.
  • hydrocarbon group examples include the following hydrocarbon groups having 1 to 20 carbon atoms.
  • specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n -Alkyl groups such as hexyl and cyclohexyl, alkenyl groups such as vinyl and propenyl, phenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl, etc. .
  • aromatic groups such as phenyl, ⁇ -
  • halogenated hydrocarbon group examples include the following halogenated hydrocarbon groups having 1 to 20 carbon atoms.
  • the halogenated hydrocarbon group having 1 to 20 carbon atoms for example, at least one hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms such as trifluoromethyl, fluorine, chlorine A group substituted with a halogen atom such as bromine, iodine, or the number of carbon atoms such as 2,3,4,5,6-pentafluorophenyl, 3,5-difluorophenyl, 3,5-ditrifluoromethylphenyl, etc. ⁇ 20 halogenated aryl groups and the like.
  • silicon-containing group examples include hydrocarbon-substituted silyl groups such as trimethylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, and triphenylsilyl, and silicon-containing groups having 1 to 20 carbon atoms.
  • oxygen-containing group examples include an oxy group; a peroxy group; a hydroxy group; a hydroperoxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; Arylalkoxy groups such as phenylethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like.
  • the sulfur-containing group includes a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl Sulfonate groups such as benzene sulfonate, triisobutyl benzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene Sulphinate groups such as ruffinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio group; arylthio group; sulfate group; sulfide
  • nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino An arylamino group such as methylimino, ethylimino group, i-propylimino group, tert-butylimino group, etc .; phenylimino, 2-methylphenylimino group, 2,6-dimethylphenylimino group 2,4,6-trimethylphenylimino group, 2-i-propylphenylimino group, 2,6-di-i-propylphenylimino group, 2,4,6-tri-i-propylphenylimino group, 2 -Tert-Buchi Arylimino groups such as
  • the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups and the like.
  • trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine
  • triarylphosphine groups such as triphenylphosphine and tolylphosphine
  • R 5 , R 8 , R 9 and R 12 are preferably a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other.
  • R 6 , R 7 , R 10 , and R 11 form a ring together with carbon atoms to which a part of the groups adjacent to each other are bonded to each other.
  • a hydrocarbon group having 1 to 20 carbon atoms which may be the same or different from each other, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group It is preferably a group, a nitrogen-containing group or a phosphorus-containing group.
  • X 1 may be the same or different from each other, and may be a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or It is a halogen atom.
  • hydrocarbon group examples include hydrocarbon groups having 1 to 20 carbon atoms
  • halogenated hydrocarbon group examples include halogenated hydrocarbon groups having 1 to 20 carbon atoms
  • oxygen-containing groups include hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy, and arylalkoxy groups such as phenylmethoxy and phenylethoxy. It is done.
  • sulfur-containing group examples include a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, and p-toluene.
  • Sulfonate groups such as sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methyl sulfonate
  • Sulfinate groups such as finate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate and pentafluorobenzene sulfinate.
  • silicon-containing group examples include hydrocarbon-substituted silyl groups such as trimethylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, and triphenylsilyl, and silicon-containing groups having 1 to 20 carbon atoms.
  • X1 is preferably a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a halogen, which may be the same or different from each other. More preferably an independently halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • Y represents a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin content.
  • the divalent hydrocarbon group is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, Alkylene groups such as 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, arylalkylene groups such as diphenylmethylene, diphenyl-1,2-ethylene, etc. Can be mentioned.
  • divalent hydrocarbon groups include dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, An alkylene group such as 1,4-cyclohexylene and an arylalkylene group such as diphenylmethylene and diphenyl-1,2-ethylene are preferred.
  • the divalent halogenated hydrocarbon group is preferably a halogenated hydrocarbon group obtained by halogenating at least one hydrogen of the divalent hydrocarbon group having 1 to 20 carbon atoms.
  • a halogenated hydrocarbon group obtained by halogenating the divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene.
  • divalent silicon-containing groups include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (iso-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p Alkyltolylene such as -tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, alkyldisilyl such as tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl, Alkyl aryl disilyl, aryl disilyl group and the like can be mentioned.
  • divalent germanium-containing group examples include groups in which silicon of the divalent silicon-containing group is replaced with germanium.
  • divalent tin-containing group examples include groups in which the silicon of the divalent silicon-containing group is substituted with tin.
  • R is a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, or an alkoxy group.
  • R is a hydrocarbon group or a halogenated hydrocarbon group
  • the same groups as the hydrocarbon groups and halogenated hydrocarbon groups exemplified for X 1 can be used.
  • R is an alkoxy group, an alkoxy group such as methoxy, ethoxy, propoxy, or butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, or naphthoxy; an arylalkoxy group such as phenylmethoxy or phenylethoxy is used. be able to.
  • Y is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent silicon-containing group, and Y is an arylalkylene group, More preferably, it is any of lucylylene groups.
  • transition metal compound represented by the general formula (V) is shown below.
  • Isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride Isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride
  • Isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride Diphenylmethylene (3,5-dimethyl-cyclopentadienyl) (fluoren
  • the transition metal compound represented by the general formula (V) can be produced according to the method described in the methods described in WO2004 / 088775 and WO2001 / 27124.
  • the transition metal compound represented by the general formula (IV) is a compound that can be suitably used in the present invention among the transition metal compounds represented by the general formula (III).
  • M is a transition metal atom in Groups 4 to 6 of the periodic table.
  • M is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably titanium, zirconium or hafnium, particularly preferably zirconium.
  • R 1 , R 2 , R 13 , R 14 , R 15 , and R 16 may be the same or different from each other, and are hydrogen or a hydrocarbon having 1 to 20 carbon atoms.
  • a group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group, and R 13 , R 14 , R 15 , R 16 May form a ring together with carbon atoms to which a part of groups adjacent to each other are bonded.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 may be the same or different and have 1 to 20 carbon atoms.
  • Hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, hydrogen atoms or halogen atoms, and adjacent to each other A part of the groups to be bonded may form a ring together with the carbon atom to which these groups are bonded.
  • hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n -Alkyl groups such as hexyl and cyclohexyl, alkenyl groups such as vinyl and propenyl, phenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl, etc. .
  • aromatic groups such as phenyl, ⁇ -naphthyl, ⁇ -naphthyl, anth
  • halogenated hydrocarbon group having 1 to 20 carbon atoms for example, at least one hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms such as trifluoromethyl, fluorine, chlorine A group substituted with a halogen atom such as bromine, iodine, or 6 carbon atoms such as 2,3,4,5,6-pentafluorophenyl, 3,5-difluorophenyl, 3,5-ditrifluoromethylphenyl, etc. ⁇ 20 halogenated aryl groups and the like.
  • silicon-containing group examples include hydrocarbon-substituted silyl groups such as trimethylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, and triphenylsilyl, and silicon-containing groups having 1 to 20 carbon atoms.
  • oxygen-containing group examples include an oxy group; a peroxy group; a hydroxy group; a hydroperoxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; Arylalkoxy groups such as phenylethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like.
  • the sulfur-containing group includes a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl Sulfonate groups such as benzene sulfonate, triisobutyl benzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene Sulphinate groups such as ruffinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio group; arylthio group; sulfate group; sulfide
  • nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino An arylamino group such as methylimino, ethylimino group, i-propylimino group, tert-butylimino group, etc .; phenylimino, 2-methylphenylimino group, 2,6-dimethylphenylimino group 2,4,6-trimethylphenylimino group, 2-i-propylphenylimino group, 2,6-di-i-propylphenylimino group, 2,4,6-tri-i-propylphenylimino group, 2 -Tert-Buchi Arylimino groups such as
  • the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups and the like.
  • trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine
  • triarylphosphine groups such as triphenylphosphine and tolylphosphine
  • R 5 , R 8 , R 9 and R 12 are preferably a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other.
  • R 1 and R 13 which may be the same or different from each other, are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, A silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group is preferred.
  • R 6 , R 7 , R 10 , and R 11 may form a ring together with carbon atoms to which a part of the groups adjacent to each other are bonded.
  • Hydrocarbon groups having 1 to 20 carbon atoms, halogenated hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, which may be the same or different from each other A group or a phosphorus-containing group is preferred.
  • R 6 , R 7 , R 10 , and R 1 may form a ring together with carbon atoms to which a part of the groups adjacent to each other are bonded to each other.
  • R 1 , R 13 , R 6 , R 7 , R 10 , and R 11 are each a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon-containing A group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group is particularly preferred.
  • R 13 is preferably an aromatic group, particularly an aryl group having 6 to 16 carbon atoms, specifically phenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthracenyl, And phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthracenyl, and phenanthryl are preferable.
  • aryl groups are halogen atoms such as fluorine, chlorine, bromine and iodine; alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl, vinyl, propenyl, Alkenyl groups such as cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl Or a hydrocarbon group having 1 to 20 carbon atoms such as trimethylsilyl, trieth
  • X 1 and X 2 which may be the same or different from each other, are a hydrocarbon group, halogenated hydrocarbon group, oxygen-containing group, sulfur-containing group, silicon-containing group, hydrogen atom or halogen. Is an atom. Specific examples of X 1 and X 2 and preferred types of substituents are the same as those of X 1 in the general formula (III).
  • Y represents a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, —O -, -CO-, -S-, -SO-, -SO 2- , -Ge-, -Sn-, -NR-, -P (R)-, -P (O) (R)-, -BR — Or —AlR— [wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, or an alkoxy group]. Specific examples of Y are the same as those of Y in the general formula (III).
  • transition metal compound represented by the general formula (IV) is shown below.
  • Dimethylsilyl ⁇ 1- (2-ethyl-4-phenylindenyl) ⁇ (fluorenyl) zirconium dichloride Dimethylsilyl ⁇ 1- (2-ethyl-4- ( ⁇ -naphthyl) indenyl) ⁇ (fluorenyl) zirconium dichloride, Dimethylsilyl ⁇ 1- (2-ethyl-4- ( ⁇ -naphthyl) indenyl) ⁇ (fluorenyl) zirconium dichloride, Dimethylsilyl ⁇ 1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl) ⁇ (fluorenyl) zirconium dichloride, Dimethylsilyl ⁇ 1- (2-ethyl-4- (5-acenaphthyl) indenyl) ⁇ (fluorenyl) zirconium dichlor
  • the transition metal compound represented by the general formula (IV) is described in J. Org. Organomet. Chem. It can be produced according to the method described in 2003, (688), 153.
  • the use of the transition metal compound represented by the general formula (I) or the general formula (II) as the transition metal compound (A) is a conjugate having a side chain double bond in the obtained copolymer.
  • the proportion of structural units derived from 1,2-addition of dienes, the proportion of structural units derived from 1,4-addition of conjugated dienes, the proportion of structural units derived from 1,3-addition of conjugated dienes, 1,2 A balance of the proportion of the total amount of structural units derived from 1,2-addition of a conjugated diene having a cyclopropane skeleton and structural units derived from 1,2-addition of a conjugated diene having a 1,2-cyclopentane skeleton; It is good in terms of physical properties.
  • the addition polymerization catalyst used in the method for producing a copolymer of the present invention includes the transition metal compounds (A) and (B-1) organometallic compounds, (B-2) organoaluminum oxy compounds, and (B-3) transitions. It consists of at least one compound (B) selected from the group consisting of compounds that react with the metal compound (A) to form ion pairs.
  • a compound that reacts with the transition metal compound (A) to form an ion pair may be referred to as an “ionized ionic compound”.
  • an organometallic compound is converted into “component (B-1)”
  • an organoaluminum oxy compound is converted into “component (B-2)”
  • a transition metal compound ( A compound that reacts with A) to form an ion pair is also referred to as “component (B-3)”.
  • components (B-1) to (B-3) will be described.
  • (B-1) Organometallic compound Specific examples of the (B-1) organometallic compound include organometallic compounds belonging to Groups 1 and 2 and Groups 12 and 13 of the Periodic Table as shown below.
  • R a and R b are the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 is Mg, Zn or Cd.
  • Examples of the organoaluminum compound belonging to (B-1a) include the following compounds.
  • General formula R a m Al (OR b ) 3-m (Wherein R a and R b represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, which may be the same or different, and m is preferably 1.5 ⁇ m ⁇
  • R a m AlH 3-m wherein R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ⁇ m ⁇ 3.
  • organoaluminum compound belonging to (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and the like.
  • Tri-n-alkylaluminum Tri-n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methyl Pentyl aluminum, tri-3-methylpentyl aluminum, tri-4-methylpentyl aluminum, tri-2-methylhexyl aluminum, tri-3- Tri-branched alkylaluminum such as tilhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritolylaluminum; diethylaluminum hydride and diisobutyl aluminum dialkyl aluminum hydride such as hydr
  • Trialkenylaluminum such as triisoprenylaluminum represented by: isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide
  • Trialkenylaluminum such as triisoprenylaluminum represented by: isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide
  • R a 2.5 Al (OR b ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented
  • a compound similar to (B-1a) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom.
  • organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom.
  • Specific examples of such a compound include (C 2 H 5 ) 2 AlN (C 2 H 5 ) Al (C 2 H 5 ) 2 .
  • Examples of the compound belonging to (B-1b) include LiAl (C 2 H 5 ) 4 and LiAl (C 7 H 15 ) 4 .
  • Other examples of the organometallic compound (B-1) include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium.
  • Chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.
  • organoaluminum compound for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can be used.
  • organometallic compounds (B-1) organoaluminum compounds are preferred.
  • the organometallic compound (B-1) as described above is used singly or in combination of two or more.
  • (B-2) Organoaluminum oxy compound The organoaluminum oxy compound (B-2) used as necessary in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum as exemplified in JP-A-2-78687. It may be an oxy compound.
  • a conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
  • a compound containing adsorbed water or a salt containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc.
  • a method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
  • the aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.
  • organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
  • the above organoaluminum compounds are used singly or in combination of two or more.
  • Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons (for example, Hydrocarbon solvents such as chlorinated products, brominated products, etc.). Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons
  • the benzene-insoluble organoaluminum oxy-compound is one in which the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, that is, with respect to benzene. Those that are insoluble or sparingly soluble are preferred.
  • organoaluminum oxy compounds examples include organoaluminum oxy compounds (G-1) containing boron represented by the following general formula (iii).
  • the organoaluminumoxy compound (G-1) containing boron represented by the general formula (iii) includes an alkyl boronic acid (G-2) represented by the following general formula (iv), R 20 -B (OH) 2 (iv) (Wherein R 20 represents the same group as described above.) It can be produced by reacting an organoaluminum compound with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of ⁇ 80 ° C. to room temperature for 1 minute to 24 hours.
  • alkyl boronic acid (G-2) represented by the general formula (iv) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, Examples thereof include n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid.
  • methyl boronic acid n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.
  • organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
  • the (B-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.
  • ((B-3) ionized ionic compound) The ionized ionic compound (B-3) is a compound that reacts with the transition metal compound (A) to form an ion pair.
  • Examples of such compounds include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, US5321106 and the like. Etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
  • examples of the Lewis acid include a compound represented by BR3 (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group, trifluoromethyl group, etc.).
  • R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group, trifluoromethyl group, etc.
  • trifluoroboron triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris
  • Examples thereof include (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.
  • Examples of the ionic compound include compounds represented by the following general formula (v).
  • examples of R 22+ include H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.
  • R 23 to R 26 each represents an organic group, preferably an aryl group or a substituted aryl group, which may be the same as or different from each other.
  • the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.
  • Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation and other N, N-dialkylanilinium cation; di (isopropyl) ammonium cation, dicyclohexylammonium cation and other dialkylammonium cation Etc.
  • phosphonium cation examples include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
  • R 22+ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.
  • ionic compounds include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.
  • trialkyl-substituted ammonium salt examples include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl).
  • N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like.
  • Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.
  • triphenylcarbenium tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl
  • Examples thereof include cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, and boron compounds represented by the following formula (vi) or (vii).
  • Et represents an ethyl group.
  • borane compound examples include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Salts of anions such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; Metal borane anion salts such as -butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III), etc. Can be mentioned.
  • carborane compound examples include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundecarborane, tri (n-butyl) ammonium 1-carbadecaborate, tri ( n-butyl) ammonium 1-carbound decaborate Caborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bro
  • the heteropoly compound is composed of one or more atoms selected from silicon, phosphorus, titanium, germanium, arsenic or tin and vanadium, niobium, molybdenum and tungsten.
  • the ionized ionic compound (B-3) as described above is used singly or in combination of two or more. Next, the manufacturing method of the copolymer of this invention is demonstrated concretely.
  • ethylene and a conjugated diene are copolymerized.
  • the conjugated diene used in the present invention is not particularly limited, but those represented by the following formula (i) are usually used.
  • R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and at least one of R 1 and R 2 is a hydrogen atom.
  • Such a conjugated diene monomer (i) may be either aromatic or aliphatic, and is not particularly limited.
  • conjugated dienes include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3-butadiene, 1- Phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene, Examples include 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, and 2-phenyl-1,3-butadiene.
  • the conjugated dienes can be used alone or in combination of two or more.
  • 1,3-butadiene is particularly preferable because it is inexpensive and has excellent copolymerizability and crosslinking efficiency.
  • the copolymer of the present invention has a vinyl group in the side chain as a side chain double bond.
  • the amount of ethylene and conjugated diene used in the method for producing a copolymer of the present invention may be an amount such that the obtained copolymer has the above-mentioned specific composition.
  • other monomers may be further used in addition to ethylene and conjugated dienes.
  • the other monomer include ⁇ -olefins having 3 to 20 carbon atoms and derivatives thereof, nonconjugated dienes and derivatives thereof, nonconjugated polyenes and derivatives thereof, and styrene and derivatives thereof.
  • Examples of the ⁇ -olefin having 3 to 20 carbon atoms and derivatives thereof include propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, -Undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl ⁇ -olefins such as -1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, and 3-phenyl Examples thereof include ⁇ -olefin derivatives such as propylene and 4-phenylbutene.
  • Styrene and its derivatives include mono- or poly-styrene such as styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, etc.
  • Alkyl styrene methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene and other functional group-containing styrene derivatives: ⁇ -methylstyrene, etc. Is mentioned.
  • Non-conjugated dienes and their derivatives include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene and the like.
  • non-conjugated polyene and derivatives thereof examples include 5,9-dimethyl-1,4,8-decatriene. These other monomers can be used alone or in combination of two or more.
  • the amount used is not particularly limited, but the molar ratio (ethylene / other monomer) between the amount of ethylene used and the amount of other monomers used is 99/1 to 40/60.
  • the molar ratio is more preferably 90/10 to 60/40, and the molar ratio is 85 / It is particularly preferably 15 to 70/30.
  • the obtained copolymer is used as an elastomer, it is particularly desirable that the molar ratio is 80/20 to 55/45.
  • ethylene and a conjugated diene are polymerized in the presence of an addition polymerization catalyst composed of the above components (A) and (B).
  • an addition polymerization catalyst composed of the above components (A) and (B).
  • a hydrocarbon solvent is generally used, but a monomer may be used as a solvent.
  • Copolymerization can be carried out by either a batch method or a continuous method.
  • the method of adding the component (A) and the component (B) to the polymerization vessel, the usage method of each component, the addition method, and the order of addition are arbitrarily selected, and the following methods are exemplified.
  • (2) A method in which a catalyst in which the component (A) and the component (B) are contacted in advance is added to the polymerization vessel.
  • the component (B) may be the same or different.
  • the component (A) is usually 10 ⁇ 13 to 10 ⁇ 2 mol, preferably 10 ⁇ 11 to 10 ⁇ 3 mol, per liter of reaction volume. Is used in such an amount.
  • the method for producing a copolymer of the present invention can provide a copolymer with high polymerization activity even when component (A) is used at a relatively low concentration.
  • component (B-1) When component (B-1) is used as component (B), the molar ratio of component (B-1) to transition metal atom (M) in component (A) [(B-1) / M ] Is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000.
  • component (B-2) When component (B-2) is used as component (B), the molar ratio of the aluminum atom in component (B-2) to the transition metal atom (M) in component (A) [(B- 2) / M] is usually 1 to 500,000, preferably 10 to 100,000.
  • component (B-3) When component (B-3) is used as component (B), the molar ratio of component (B-3) to transition metal atom (M) in component (A) [(B-3) / M ] Is usually used in an amount of 1 to 10, preferably 1 to 5.
  • the polymerization temperature is usually in the range of ⁇ 50 to 200 ° C., preferably 0 to 170 ° C.
  • the polymerization pressure is usually from normal pressure to 100 kg / cm 2 , preferably from normal pressure to 50 kg / cm 2 , and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. it can. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.
  • the reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 1.5. It's time.
  • the molecular weight and molecular weight distribution of the copolymer obtained by the method for producing a copolymer of the present invention can be adjusted by using a molecular weight regulator such as hydrogen.
  • the molecular weight and molecular weight distribution of the copolymer obtained by the method for producing a copolymer of the present invention can be adjusted by changing the polymerization temperature.
  • the molecular weight and molecular weight distribution of the copolymer obtained in the present invention are adjusted by changing the amount of the organometallic compound (B-1), the organoaluminum oxy compound (B-2), or both. You can also In general, in order to lower the molecular weight, the molar ratio of (organoaluminum compound / transition metal) is increased, and in order to narrow the molecular weight distribution (number of moles of organoaluminum compound / number of moles of polymer produced) is increased. Can be done.
  • the molecular weight and molecular weight distribution of the copolymer obtained by the method for producing a copolymer of the present invention can also be adjusted by changing the copolymer concentration in the polymerization solution.
  • the copolymer concentration in the polymerization solution is 0.01 to 500 g / L, preferably 0.1 to 100 g / L, and more preferably 1 ⁇ 20 g / L.
  • the copolymer of the present invention can be variously modified when it has a double bond in the side chain.
  • the modification of the copolymer of the present invention include peroxide modification.
  • peroxide modification the double bond of the side chain which the copolymer of this invention has can be epoxidized, and the epoxy group rich in reactivity can be introduce
  • the copolymer of the present invention or a modified product thereof can be used as a thermosetting resin or a reactive resin. Further, since the copolymer of the present invention has a double bond in the side chain, it can be used for Diels-Alder reaction, Michael addition reaction, and the like.
  • the modified product examples include a modified product obtained by modifying part or all of the double bond of the copolymer with an unsaturated carboxylic acid, a derivative thereof, or an aromatic vinyl compound.
  • the modified product is excellent in adhesiveness with polyester resin, polycarbonate resin, olefin / vinyl acetate copolymer saponified product, polyolefin, and the like, and can be used for applications such as an adhesive between these resins.
  • the modified amount of the modified product ([modified product (weight) -copolymer (weight)] / [copolymer (weight)] ⁇ 100) is preferably in the range of 0.01 to 30% by weight. .
  • the copolymer of the present invention can be crosslinked in the presence of an organic peroxide to obtain a crosslinked product.
  • a highly reactive double bond is present in the side chain. Therefore, the amount of the radical initiator used when modifying the copolymer is changed in the side chain. It can reduce compared with the copolymer in which a double bond does not exist.
  • a radical generated by a hydrogen abstraction reaction from the copolymer by an initiator is used as an initiation point of the reaction. Yes.
  • the probability of a hydrogen abstraction reaction per mole of initiator is not so high, so that a copolymer with no double bonds in the side chain will have a large amount of initiation to obtain a sufficient amount of starting point for the reaction.
  • An agent is required.
  • the reaction of the polymer with the initiator generally decreases the molecular weight of the polymer, particularly when the main chain contains an unsaturated bond, the molecular weight significantly decreases, and the crosslinked product. Increases surface tackiness.
  • the copolymer according to the present invention since a double bond is present in the side chain, the amount of radical initiator used can be reduced, and at the same time, radicals generated during modification are mainly side chain. Since the main chain does not contain a substantially unsaturated bond, the main chain decomposition reaction is suppressed, and hence the molecular weight is also prevented from being lowered. As a result, the obtained crosslinked product has low adhesiveness on the surface of the crosslinked product, does not have abnormal foaming inside, and is excellent in heat aging resistance (heat resistance) and sag resistance.
  • a copolymer having substantially no unsaturated bond in the main chain, a cyclic structure in the main chain, and a double bond in the side chain is excellent in weather resistance, heat resistance, oil resistance, etc., and has a glass transition point.
  • it is excellent in cold resistance, excellent in crosslinking efficiency and modification efficiency, particularly in the case of using an organic peroxide, excellent in crosslinking efficiency and modification efficiency, and is capable of sulfur crosslinking.
  • the cross-linked product obtained when using organic peroxides has low adhesiveness on the cross-linked product surface, no abnormal foaming inside, and heat aging resistance (heat resistance) and sag resistance. Also excellent.
  • molecular weight was calculated
  • Pretreatment of sample> After 30 mg of the sample was completely dissolved in 20 mL of o-dichlorobenzene at 145 ° C., the solution was filtered through a sintered filter having a pore diameter of 0.45 mm as an analysis sample.
  • ⁇ measuring device DSC-60 (manufactured by Shimadzu Corporation)
  • ⁇ Measurement condition> In a N 2 (nitrogen) atmosphere, the temperature is raised from room temperature to 200 ° C. at a rate of 50 ° C./min and held for 5 minutes, then the temperature is lowered to ⁇ 100 ° C. at a rate of 10 ° C./min and held for 5 minutes did. And it heated up to 200 degreeC with the temperature increase rate of 10 degree-C / min.
  • the glass transition point and melting point shown in Examples and Comparative Examples show values from endothermic curves in the second scan.
  • Example 1 Toluene and triisobutylaluminum (also referred to as iBu3Al) 0.2 mmol in a reactor with a volume of 15 mL sufficiently purged with nitrogen (Argonaute's parallel pressure catalytic reactor (trade name Endeavor) equipped with 8 parallel reactors)
  • the liquid phase and the gas phase were saturated with 1.0 kg / cm 2 ⁇ G of 1,3-butadiene at 30 ° C.
  • the mixture is heated to 40 ° C. to set the reactor internal pressure to 1.1 kg / cm 2 ⁇ G, and further pressurized with ethylene gas so that the reactor internal pressure becomes 2.0 kg / cm 2 ⁇ G.
  • the gas phase was saturated.
  • the total amount of toluene charged was 5 mL. Ethylene gas was continuously fed so that the total pressure was maintained at 2.0 kg / cm 2 ⁇ G and reacted at 40 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the reaction product was suspended in hexane, washed with dilute hydrochloric acid, concentrated, and dried under reduced pressure at 20 ° C. for 10 hours to obtain an ethylene / 1,3-butadiene copolymer.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.04 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.05 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Example 2 Toluene and dry methylaluminoxane (Methylaluminoxane (20% Albemarle) (20 units equipped with Argonaute's parallel pressure catalytic reactor (trade name Endeavor), equipped with 8 parallel reactors) were fully purged with nitrogen.
  • the liquid phase and gas phase were saturated with butadiene 1.0 kg / cm 2 ⁇ G.
  • the mixture is heated to 40 ° C. to set the reactor internal pressure to 1.1 kg / cm 2 ⁇ G, and further pressurized with ethylene gas so that the reactor internal pressure becomes 9.0 kg / cm 2 ⁇ G.
  • the gas phase was saturated.
  • the yield of ethylene / 1,3-butadiene copolymer was 1.29 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 1.93 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • iBu3Al triisobutylaluminum
  • the yield of ethylene / 1,3-butadiene copolymer was 0.24 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 1.47 kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Example 4 In Example 2, the liquid phase and the gas phase were saturated so that the internal pressure of the reactor after pressurization with ethylene gas was 2.0 kg / cm 2 ⁇ G, and Organometallics 2004, 23, p.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.53 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 3.21 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Example 5 In Example 4, after the liquid phase and the gas phase were saturated with 1.0 kg / cm 2 ⁇ G of 1,3-butadiene at 30 ° C., the mixture was heated to 60 ° C., and the internal pressure of the reactor was 1.5 kg / and cm 2 ⁇ G, the internal pressure of the reactor after pressurization with ethylene gas to saturate the liquid phase and the gas phase such that 2.0kg / cm 2 ⁇ G, a total pressure of 2.0kg / cm 2 ⁇ G Polymerization and post-treatment were performed in the same manner as in Example 4 except that the polymerization was carried out at 60 ° C. while continuously feeding ethylene gas so as to maintain an ethylene / 1,3-butadiene copolymer.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.03 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.18 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Example 1 In Example 1, the amount of added triisobutylaluminum was 0.05 mmol, and dimethylsilyl ⁇ 1- (2-methyl-4,5-benzoindenyl) ⁇ (2,7-ditert-butylfluorenyl) Instead of 0.2 mL of a toluene solution (10 mmol / L) of zirconium dichloride (complex 1), Eur. Patent.
  • 416, 815 A2 synthesized according to the method described in 416, 815 A2, [(tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silane] titanium dichloride ((tert-butyllamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride4)
  • Polymerization and post-treatment were performed in the same manner as in Example 1 except that 0.2 mL of the solution (2.5 mmol / L) was used to obtain an ethylene / 1,3-butadiene copolymer.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.18 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 1.08 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Example 2 In Example 1, the amount of added triisobutylaluminum was 0.05 mmol, and dimethylsilyl ⁇ 1- (2-methyl-4,5-benzoindenyl) ⁇ (2,7-ditert-butylfluorenyl) Instead of 0.2 mL of a toluene solution (10 mmol / L) of zirconium dichloride (complex 1), Macromolecules 1998, 31, p.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.37 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 2.24 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.13 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.80 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • the yield of ethylene / 1,3-butadiene copolymer was 1.70 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 10.20 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Example 3 instead of [hydrotris (3-mesitylpyrazol-1-yl)] borate zirconium trichloride ([hydrotris (3-mesylpyrazol-1-yl)] borate zirconium trichloride) (complex 3), Eur. Patent.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.18 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 1.08 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Example 3 instead of [hydrotris (3-mesitylpyrazol-1-yl)] borate zirconium trichloride ([hydrotris (3-mesylpyrazol-1-yl)] borate zirconium trichloride (complex 3), Macromolecules 1998 , 31, p. Example 3 except that [(tert-butylamido) dimethyl (fluorenyl) silane] titanium dimethyl ((tert-butyramide) dimethylethyl (fluorenyl) silanenetium dimethyl) (complex 5) synthesized according to the method described in 3184 was used. Polymerization and post-treatment were carried out to obtain an ethylene / 1,3-butadiene copolymer.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.37 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 2.24 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Example 7 In Example 4, instead of [hydrotris (3-mesitylpyrazol-1-yl)] borate zirconium trichloride ([hydrotris (3-mesylpyrazole-1-yl)] borate zirconium trichloride (complex 3), Macromolecules 1998 , 31, p. Example 3 except that [(tert-butylamido) dimethyl (fluorenyl) silane] titanium dimethyl ((tert-butyramido) dimethyl (fluorenyl) silanetium dimethyl) (complex 5) synthesized according to the method described in 3184 was used. Polymerization and post-treatment were carried out to obtain an ethylene / 1,3-butadiene copolymer.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.13 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.80 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Example 8 In Example 2, rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride) Instead of (Complex 2), Macromolecules 1998, 31, p. Example 3 except that [(tert-butylamido) dimethyl (fluorenyl) silane] titanium dimethyl ((tert-butyramide) dimethyl (fluorenyl) silanetium dimethyl) (complex 5) synthesized according to the method described in 3184 was used. Polymerization and post-treatment were carried out to obtain an ethylene / 1,3-butadiene copolymer.
  • the yield of ethylene / 1,3-butadiene copolymer was 1.70 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 10.20 [kg / (mmol ⁇ h)]. The results are shown in Tables 1 and 2.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was maintained at 8.0 kg / cm 2 ⁇ G, and the reaction was carried out at 60 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, the polymer was precipitated and filtered, and then dried under reduced pressure at 20 ° C. for 24 hours to obtain an ethylene / 1,3-butadiene copolymer. Obtained.
  • the yield of ethylene / 1,3-butadiene copolymer was 13.848 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 10.39 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 7 In Example 6, instead of using 8.0 mL of a toluene solution (0.5 mmol / L) of isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride (complex 6), Diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride (complex) synthesized according to the method described in WO 2004/087775 pamphlet Polymerization and post-treatment were performed in the same manner as in Example 6 except that 8.0 mL of the toluene solution of 7) (0.5 mmol / L) was used to obtain an ethylene / 1,3-butadiene copolymer.
  • 8.0 mL of the toluene solution of 7 0.5 mmol / L
  • the yield of ethylene / 1,3-butadiene copolymer was 2.193 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 1.64 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 8 In Example 6, instead of using 8.0 mL of a toluene solution (0.5 mmol / L) of isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride (complex 6), J. et al. Organomet. Chem.
  • the yield of ethylene / 1,3-butadiene copolymer was 4.294 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 3.22 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was kept at 4.0 kg / cm 2 ⁇ G, and the reaction was carried out at 40 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, and the polymer was precipitated and filtered, followed by drying under reduced pressure at 20 ° C. for 10 hours to obtain an ethylene / 1,3-butadiene copolymer. Obtained.
  • the yield of ethylene / 1,3-butadiene copolymer was 13.81 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.69 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 10 In Example 9, the internal pressure of the autoclave after being saturate the liquid phase and the gas phase 1,3-butadiene was 0.8kg / cm 2 ⁇ G at 0.3kg / cm 2 ⁇ G, 40 °C at 10 ° C. Instead, the internal pressure at 10 ° C. was 0.7 kg / cm 2 ⁇ G and the internal pressure at 40 ° C. was 1.3 kg / cm 2 ⁇ G (100 g of 1,3-butadiene was charged). Polymerization and post-treatment were performed in the same manner as in Example 9 except that the internal pressure of the autoclave after saturation of the phase was 8.0 kg / cm 2 ⁇ G, and an ethylene / 1,3-butadiene copolymer was obtained. Obtained.
  • the yield of ethylene / 1,3-butadiene copolymer was 34.358 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 1.72 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 11 In Example 9, instead of using 12.0 mL of a toluene solution (5.0 mmol / L) of isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride (complex 6), Diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride (complex) synthesized according to the method described in WO 2004/087775 pamphlet Polymerization and post-treatment were performed in the same manner as in Example 9 except that 12.0 mL of the toluene solution (5.0 mmol / L) of 7) was used to obtain an ethylene / 1,3-butadiene copolymer.
  • the yield of ethylene / 1,3-butadiene copolymer was 0.28 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.01 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 12 In Example 9, instead of using 12.0 mL of a toluene solution (5.0 mmol / L) of isopropylidene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride (complex 6), J. et al. Organomet. Chem.
  • the yield of ethylene / 1,3-butadiene copolymer was 1.931 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.10 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was maintained at 8.0 kg / cm 2 ⁇ G, and the reaction was carried out at 60 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, the polymer was precipitated and filtered, and then dried under reduced pressure at 20 ° C. for 24 hours to obtain an ethylene / 1,3-butadiene copolymer. Obtained.
  • the yield of ethylene / 1,3-butadiene copolymer was 9.42 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 14.13 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 14 In Example 13, Organometallics 1994, 13, p. Rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4-phenyllindenyl)] synthesized according to the method described in 954 Instead of using 4.0 mL of a toluene solution (0.5 mmol / L) of zirconium dichloride (complex 2), rac-dimethylsilyl-bis ⁇ 1- (2-n -Propyl-4- (9-phenanthryl) indenyl) ⁇ zirconium dichloride (rac-Dimethylsilyl-bis [1- (2-n-propyl-4- (9-phenthryllinyl))] zirconium dic polymerized and post-treated in the same manner as in Example 13 except that 4.0 mL of a toluene solution (0.5 mmol / L)
  • the yield of ethylene / 1,3-butadiene copolymer was 2.43 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 3.64 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 15 In Example 13, Organometallics 1994, 13, p. Rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4-phenyllindenyl)] synthesized according to the method described in 954 Instead of using 4.0 mL of a toluene solution (0.5 mmol / L) of zirconium dichloride (complex 2), rac-dimethylsilyl-bis [1- (2-ethyl) synthesized according to the method described in JP-A-7-286005 -4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-ethyl-4-phenyllindenyl)] zirconium dichloride) (complex 9) in toluene solution (0 Except for using 5 mmol / L) 4.0 mL of perform
  • the yield of ethylene / 1,3-butadiene copolymer was 4.16 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 6.23 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 16 In Example 13, Organometallics 1994, 13, p. Rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4-phenyllindenyl)] synthesized according to the method described in 954 Instead of using 4.0 mL of a toluene solution (0.5 mmol / L) of zirconium dichloride (complex 2), rac-dimethylsilyl-bis ⁇ 1- (2-methyl) synthesized according to the method described in JP-A-7-13812 -4- (p-trifluoromethylphenyl) indenyl) ⁇ zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4- (p-trifluorophenyl) indenyl)) zirconia m dichloride) (complex 10), except that 4.0 mL of a tol
  • the yield of ethylene / 1,3-butadiene copolymer was 2.26 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 3.39 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 17 In Example 13, Organometallics 1994, 13, p. Rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4-phenyllindenyl)] synthesized according to the method described in 954 Instead of using 4.0 mL of a toluene solution (0.5 mmol / L) of zirconium dichloride (complex 2), rac-dimethylsilyl-bis ⁇ 1- (2-n -Propyl-4- (1-naphthyl) indenyl) ⁇ zirconium dichloride (rac-Dimethylsilyl-bis [1- (2-n-propyl-4- (1-naphthyllindenyl))] zirconium dichlorid ) Polymerization and post-treatment were carried out in the same manner as in Example 13 except that 4.0 mL of a to
  • the yield of ethylene / 1,3-butadiene copolymer was 4.56 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 6.84 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 18 In Example 13, Organometallics 1994, 13, p. Rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4-phenyllindenyl)] synthesized according to the method described in 954 rac- (methyl) (phenyl) silyl-bis ⁇ 1 synthesized according to the method described in JP-A-7-286005 instead of using 4.0 mL of a toluene solution (0.5 mmol / L) of zirconium dichloride (complex 2) -(6-Chloro-2-ethyl-4- (9-phenanthryl) indenyl) ⁇ zirconium dichloride, (rac- (Methyl) (phenyl) silyl-bis [1- (6-chloro-2-ethyl-4- ( 9-phenanthr yl-indenyl))] zi
  • the yield of ethylene / 1,3-butadiene copolymer was 0.69 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 1.04 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 19 In Example 13, Organometallics 1994, 13, p. Rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4-phenyllindenyl)] synthesized according to the method described in 954 Instead of using 4.0 mL of a toluene solution (0.5 mmol / L) of zirconium dichloride (complex 2), rac-dimethylsilyl- ⁇ 1- (2-ethyl-) synthesized according to the method described in JP-A-10-087716 4- (5- (2,2-dimethyl-2,3-dihydro-1H-cyclopentaneaphthalenyl)) indenyl) ⁇ ⁇ 1- (2-n-propyl-4- (5- (2,2 -Dimethyl-2,3-dihydro-1H-cyclopentanenaphthalenyl)) indenyl
  • the yield of ethylene / 1,3-butadiene copolymer was 3.53 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 5.29 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 20 In Example 13, Organometallics 1994, 13, p. Rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4-phenyllindenyl)] synthesized according to the method described in 954 Instead of using 4.0 mL of a toluene solution (0.5 mmol / L) of zirconium dichloride (complex 2), Organometallics 1994, 13, p.
  • the yield of ethylene / 1,3-butadiene copolymer was 29.94 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 44.91 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was maintained at 8.0 kg / cm 2 ⁇ G and reacted at 40 ° C. for 20 minutes, and then the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, the polymer was precipitated and filtered, and then dried under reduced pressure at 20 ° C. for 24 hours to obtain an ethylene / 1,3-butadiene copolymer. Obtained.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was maintained at 8.0 kg / cm 2 ⁇ G, and the reaction was carried out at 60 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, the polymer was precipitated and filtered, and then dried under reduced pressure at 20 ° C. for 24 hours to obtain an ethylene / 1,3-butadiene copolymer. Obtained.
  • the yield of ethylene / 1,3-butadiene copolymer was 33.78 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 12.67 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • rac-dimethylsilyl-bis ⁇ 1- (2-n-propyl) synthesized in accordance with the method described in JP-A-7-286005 was placed in an autoclave and sufficiently substituted with nitrogen in a catalyst charging pot having an internal volume of 20 ml.
  • -4- (9-phenanthryl) indenyl) ⁇ zirconium dichloride rac-Dimethylsilyl-bis [1- (2-n-propyryl-4- (9-phenanthrylindyl))] zirconium dichloride (complex 8) in toluene solution (0) 0.5 mmol / L) was added, and the autoclave was charged with nitrogen under pressure to initiate polymerization.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was maintained at 8.0 kg / cm 2 ⁇ G and reacted at 40 ° C. for 20 minutes, and then the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, the polymer was precipitated and filtered, and then dried under reduced pressure at 20 ° C. for 24 hours to obtain an ethylene / 1,3-butadiene copolymer. Obtained.
  • the yield of ethylene / 1,3-butadiene copolymer was 4.80 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 1.80 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 24 In Example 23, except that the amount of 1,3-butadiene charged was changed from 50 g to 60 g and the polymerization temperature was changed from 40 ° C. to 60 ° C. (autoclave internal pressure at 60 ° C. 3.1 kg / cm 2 ⁇ G). Polymerization and post-treatment were performed in the same manner as in Example 23 to obtain an ethylene / 1,3-butadiene copolymer.
  • the yield of ethylene / 1,3-butadiene copolymer was 1.05 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.39 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 25 In Example 22, Organometallics 1994, 13, p. Rac-dimethylsilyl-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride (rac-dimethylsilyl-bis [1- (2-methyl-4-phenyllindenyl)] synthesized according to the method described in 954 rac-dimethylsilyl-bis ⁇ 1- (2-n) synthesized according to the method described in JP-A-7-286005 instead of using 16.0 mL of a toluene solution (0.5 mmol / L) of zirconium dichloride (complex 2) -Propyl-4- (9-phenanthryl) indenyl) ⁇ zirconium dichloride (rac-Dimethylsilyl-bis [1- (2-n-propyl-4- (9-phenthryllinyl))] zirconium di polymerization and post-treatment were carried out in the same manner as in Example 22 except that 16.0
  • the yield of ethylene / 1,3-butadiene copolymer was 13.38 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 5.02 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 26 In Example 25, polymerization and post-treatment were performed in the same manner as in Example 25 except that the amount of charged hydrogen was changed to 372 mL (20 ° C., volume at normal pressure), and an ethylene / 1,3-butadiene copolymer was obtained. Got.
  • the yield of ethylene / 1,3-butadiene copolymer was 11.49 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 4.310 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 27 polymerization and post-treatment were performed in the same manner as in Example 26 except that the amount of 1,3-butadiene charged was changed from 40 g to 50 g (internal pressure 3.4 kg / cm 2 ⁇ G at 60 ° C.). And an ethylene / 1,3-butadiene copolymer was obtained.
  • the yield of ethylene / 1,3-butadiene copolymer was 7.03 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 2.64 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 28 In Example 27, rac-dimethylsilyl-bis ⁇ 1- (2-n-propyl-4- (9-phenanthryl) indenyl) ⁇ zirconium dichloride (rac-dimethylsilyl-) synthesized according to the method described in JP-A-7-286005 Instead of using 16.0 mL of a toluene solution (0.5 mmol / L) of bis [1- (2-n-propyryl-4- (9-phenanthrylindyl))] zirconium dichloride) (complex 8), JP-A-7-286005 Rac-dimethylsilyl-bis ⁇ 1- (2-ethyl-4- (9-phenanthryl) indenyl) ⁇ zirconium dichloride (rac-dimethylsilyl-bis [1- (2-ethyl-4- ( 9- phenanthrylindyl))] zirconium dichloride) (complex 15), except that 16.0 mL of a to
  • the yield of ethylene / 1,3-butadiene copolymer was 6.23 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 2.34 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was maintained at 8.0 kg / cm 2 ⁇ G, and the reaction was carried out at 60 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, and the polymer was precipitated and filtered, followed by drying under reduced pressure at 20 ° C. for 10 hours to obtain an ethylene / 1,3-butadiene copolymer. Obtained. The results are shown in Tables 3 and 4.
  • the yield of ethylene / 1,3-butadiene copolymer was 20.0.013 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 3.00 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was kept at 4.0 kg / cm 2 ⁇ G, and the reaction was carried out at 40 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, and the polymer was precipitated and filtered, followed by drying under reduced pressure at 20 ° C. for 10 hours to obtain an ethylene / 1,3-butadiene copolymer. Obtained.
  • the yield of ethylene / 1,3-butadiene copolymer was 3.243 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.49 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • rac-dimethylsilyl-bis ⁇ 1- (2-n-propyl) synthesized in accordance with the method described in JP-A-7-286005 was placed in an autoclave and sufficiently substituted with nitrogen in a catalyst charging pot having an internal volume of 20 ml.
  • -4- (9-phenanthryl) indenyl) ⁇ zirconium dichloride rac-dimethylsilyl-bis [1- (2-n-propyryl-4- (9-phenanthrylindenyl))] zirconium dichloride (complex 8) in toluene solution (5) 1.0 mmol / L) was added and the autoclave was charged with nitrogen under pressure to initiate polymerization.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was kept at 4.0 kg / cm 2 ⁇ G, and the reaction was carried out at 40 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, and the polymer was precipitated and filtered, followed by drying under reduced pressure at 20 ° C. for 10 hours to obtain an ethylene / 1,3-butadiene copolymer. Obtained. The results are shown in Tables 3 and 4.
  • the yield of ethylene / 1,3-butadiene copolymer was 1.409 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.07 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was maintained at 8.0 kg / cm 2 ⁇ G, and the reaction was carried out at 60 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, and the polymer was precipitated and filtered, followed by drying under reduced pressure at 20 ° C. for 24 hours to obtain ethylene / octene / 1,3-butadiene copolymer. Coalescence was obtained.
  • the yield of ethylene / octene / 1,3-butadiene copolymer was 7.40 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 2.78 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Example 33 In Example 32, the polymerization temperature was changed from 40 ° C. to 60 ° C. (internal pressure of autoclave at 60 ° C .: 2.4 kg / cm 2 ⁇ G), and the amount of hydrogen charged was changed from 248 mL to 372 mL (volume at 20 ° C., normal pressure). Except for the change, polymerization and post-treatment were carried out in the same manner as in Example 32 to obtain an ethylene / octene / 1,3-butadiene copolymer.
  • the yield of ethylene / octene / 1,3-butadiene copolymer was 13.83 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 5.19 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • Al methylaluminoxane
  • the liquid phase and the gas phase are saturated so that the internal pressure of the autoclave becomes 3.4 kg / cm 2 ⁇ G by pressurizing with propylene gas, and then further pressurized with ethylene gas so that the internal pressure of the autoclave becomes 8.
  • the liquid phase and the gas phase were saturated so as to be 0 kg / cm 2 ⁇ G.
  • rac-dimethylsilyl-bis ⁇ 1- (2-n-propyl) synthesized in accordance with the method described in JP-A-7-286005 was placed in an autoclave and sufficiently substituted with nitrogen in a catalyst charging pot having an internal volume of 20 ml.
  • -4- (9-phenanthryl) indenyl) ⁇ zirconium dichloride rac-Dimethylsilyl-bis [1- (2-n-propyryl-4- (9-phenanthrylindyl))] zirconium dichloride (complex 8) in toluene solution (0) 0.5 mmol / L) was added and the autoclave was charged with nitrogen under pressure to initiate polymerization.
  • Ethylene gas was continuously fed so that the internal pressure of the autoclave was maintained at 8.0 kg / cm 2 ⁇ G, and the reaction was carried out at 60 ° C. for 20 minutes. Then, a small amount of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer solution was added to a large excess of methanol to which hydrochloric acid was added, and the polymer was precipitated and filtered, followed by drying under reduced pressure at 20 ° C. for 20 hours to obtain ethylene / propylene / 1,3-butadiene copolymer. Coalescence was obtained. The results are shown in Tables 3 and 4.
  • the yield of ethylene / 1,3-butadiene copolymer was 7.61 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 5.71 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • a catalyst charging pot having an internal volume of 20 ml, charged with 0.0 mmol, not charged with hydrogen, mounted in an autoclave, and sufficiently purged with nitrogen was synthesized according to the method described in International Publication No. 2004/088775.
  • the yield of ethylene / 1,3-butadiene copolymer was 5.69 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 4.26 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • the yield of ethylene / 1,3-butadiene copolymer was 1.22 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 0.92 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • a catalyst charging pot having an internal volume of 20 ml, charged with 0.0 mmol, not charged with hydrogen, mounted in an autoclave, and sufficiently purged with nitrogen was synthesized according to the method described in International Publication No. 2004/088775.
  • the yield of ethylene / 1,3-butadiene copolymer was 86.48 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 64.86 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • the yield of ethylene / 1,3-butadiene copolymer was 243.86 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 20.32 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • the yield of ethylene / 1,3-butadiene copolymer was 1.53 g.
  • the activity of the reaction (yield per unit time [kg / h] / number of moles of complex [mmol]) was 1.15 [kg / (mmol ⁇ h)]. The results are shown in Tables 3 and 4.
  • EP0416815 In (A2) was synthesized according to the method of placing (tert- butylamido) dimethyl (tetramethyl-eta 5 - cyclopentadienyl) was added 4.0mL toluene solution (0.5 mmol / L) silane titanium dichloride (complex 4), the autoclave with nitrogen Example 27, except that a toluene solution (4.0 mmol / L) of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added in an amount of 6.0 equivalents to Ti and polymerization was started. Polymerization and post-treatment were performed in the same manner as described above to obtain an ethylene / 1,3-buta
  • Example 35 (Hot air bridge) About the resin composition which mix
  • Example 35 Each component shown in Table 3 below was blended in 20 g of the copolymer obtained in Example 29 in the proportions shown in the same table, and these were kneaded using a 6-inch open roll (manufactured by Nippon Roll Co., Ltd.). Then, a resin composition was prepared.
  • the crosslinking state at a temperature of 170 ° C. was measured using a crosslinking state measuring machine RPA2000P (manufactured by ALPHA TECHNOLOGIES, RUBBER PROCESS ANALYZER RPA2000P) to evaluate the crosslinking state.
  • RPA2000P manufactured by ALPHA TECHNOLOGIES, RUBBER PROCESS ANALYZER RPA2000P
  • Example 36 In total 89 g of the resin obtained by combining the copolymer obtained in Example 33 and the copolymer manufactured under the same conditions, each component shown in Table 3 below was blended in the proportions shown in the same table, A resin composition was prepared by kneading using a 6-inch open roll (manufactured by Nippon Roll Co., Ltd.).
  • the crosslinking state at a temperature of 170 ° C. was measured using a crosslinking state measuring machine RPA2000P, and the crosslinking state was evaluated.
  • the results are shown in Table 5 and FIG.
  • the crosslinking state at a temperature of 170 ° C. was measured using a crosslinking state measuring machine RPA2000P, and the crosslinking state was evaluated.
  • the results are shown in Table 5 and FIG.
  • the crosslinking state at a temperature of 170 ° C. was measured using a crosslinking state measuring machine RPA2000P, and the crosslinking state was evaluated.
  • the results are shown in Table 5 and FIG.
  • the ethylene / butadiene copolymer and the ethylene / octene / butadiene copolymer obtained in the present invention showed a rapid increase in torque and excellent cross-linking reactivity.
  • the ethylene / propylene / VNB copolymer and the ethylene / propylene / ENB copolymer had almost no increase in torque and were inferior in crosslinking reactivity.
  • the copolymer of the present invention is excellent in weather resistance, heat resistance, oil resistance, economy, etc., has a low glass transition point and excellent cold resistance, and also has excellent crosslinking efficiency and modification efficiency, and particularly uses an organic peroxide. In this case, the crosslinking efficiency and modification efficiency are excellent, and sulfur crosslinking is also possible.
  • the method for producing a copolymer of the present invention can industrially produce the copolymer at low cost and economical efficiency.

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Abstract

L'invention porte sur un copolymère possédant une double liaison dans sa chaîne latérale et ne possédant sensiblement aucune liaison insaturée dans sa chaîne principale, ou sur un copolymère présentant une structure cyclique et ne possédant sensiblement pas de liaison insaturée dans sa chaîne principale ; et sur un procédé de synthèse du copolymère économiquement avantageux. Le copolymère est obtenu par copolymérisation au moins de l'éthylène et des diènes conjugués, la teneur en unités constitutives issues des diènes conjugués étant de 1 à 90 % en moles, la teneur en unités constitutives issues de l'ajout 1,2 d'un diène conjugué possédant une double liaison dans sa chaîne latérale étant de 0 à 90 % en moles, la teneur en unités constitutives issues de l'ajout 1,4 des diènes conjugués étant de 0 à 3 % en moles, la teneur en unités constitutives issues de l'ajout 1,3 des diènes conjugués étant de 0 à 3 % en moles, et la teneur totale en unités constitutives issues de l'ajout 1,2 d'un diène conjugué possédant un squelette 1,2-cyclopropane et en unités constitutives issues de l'ajout 1,2 d'un diène conjugué présentant un squelette 1,2-cyclopentane étant de 4 à 100 % en moles.
PCT/JP2010/055759 2009-03-30 2010-03-30 Copolymère d'oléfine et de diène conjugué et son procédé de fabrication WO2010113975A1 (fr)

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SG2011070323A SG174602A1 (en) 2009-03-30 2010-03-30 Copolymer of olefin and conjugated diene, and process for producing same
EP10758746.1A EP2415792B1 (fr) 2009-03-30 2010-03-30 Copolymère d'oléfine et de diène conjugué et son procédé de fabrication
CN201080012424.XA CN102356100B (zh) 2009-03-30 2010-03-30 烯烃与共轭二烯的共聚物及其制备方法
JP2011507234A JP5557835B2 (ja) 2009-03-30 2010-03-30 オレフィンと共役ジエンとの共重合体、およびその製造方法
KR1020117024074A KR101359198B1 (ko) 2009-03-30 2010-03-30 올레핀과 공액 다이엔의 공중합체, 및 그의 제조 방법
US13/260,237 US8513368B2 (en) 2009-03-30 2010-03-30 Copolymer of olefin and conjugated diene, and process for producing the same

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JP2012031318A (ja) * 2010-07-30 2012-02-16 Bridgestone Corp 共役ジエン化合物と非共役オレフィンとの共重合体
JP2012131965A (ja) * 2010-11-30 2012-07-12 Bridgestone Corp 共重合体及びその製造方法、並びに、ゴム組成物、架橋ゴム組成物、及びタイヤ
JP2017516911A (ja) * 2014-05-31 2017-06-22 株式会社ブリヂストン 金属錯体触媒、それを使用した重合方法、及びそのポリマー生成物
WO2019111494A1 (fr) * 2017-12-05 2019-06-13 株式会社ブリヂストン Procédé de production de copolymère multiséquencé
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JP5557835B2 (ja) 2014-07-23
EP2415792A1 (fr) 2012-02-08
SG174602A1 (en) 2011-11-28
KR101359198B1 (ko) 2014-02-05
CN102356100B (zh) 2014-01-08
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US8513368B2 (en) 2013-08-20
EP2415792A4 (fr) 2012-09-26

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